EP1333909B1 - Katalysatorzusammensetzung zur reinigung von abgasen - Google Patents
Katalysatorzusammensetzung zur reinigung von abgasen Download PDFInfo
- Publication number
- EP1333909B1 EP1333909B1 EP01970694A EP01970694A EP1333909B1 EP 1333909 B1 EP1333909 B1 EP 1333909B1 EP 01970694 A EP01970694 A EP 01970694A EP 01970694 A EP01970694 A EP 01970694A EP 1333909 B1 EP1333909 B1 EP 1333909B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amount
- alumina
- metal component
- catalyst composition
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 claims abstract description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 50
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 42
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 32
- 239000010970 precious metal Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 29
- 239000003870 refractory metal Substances 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 24
- 150000004706 metal oxides Chemical class 0.000 claims description 24
- 229910052703 rhodium Inorganic materials 0.000 claims description 24
- 239000010948 rhodium Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011214 refractory ceramic Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 abstract description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052772 Samarium Inorganic materials 0.000 abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 9
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 description 24
- -1 methane hydrocarbons Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 241000907788 Cordia gerascanthus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- LSCGKEXQUPQEQB-UHFFFAOYSA-N cerium samarium zirconium Chemical compound [Ce][Zr][Sm] LSCGKEXQUPQEQB-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000011238 particulate composite Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to a catalyst composition containing a composite of cerium, zirconium and samarium components as well as the use of such catalyst composition for the treatment of a gas stream to reduce contaminants contained therein. More specifically, the present invention is concerned with catalyst compositions containing such composite of the type generally referred to as three-way conversion or "TWC" and a process of substantially simultaneously catalysing the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides present in gas streams, particularly exhaust gas streams produced by internal combustion engines.
- TWC three-way conversion
- TWC Three-way conversion catalysts
- Emission standards for unburned hydrocarbons, carbon monoxide and nitrogen oxide contaminants have been set by various governments and must be met by older as well as new vehicles.
- catalytic converters containing a TWC catalyst are located in the exhaust gas line of internal combustion engines. Such catalysts promote the oxidation by oxygen in the exhaust gas stream of unburned hydrocarbons and carbon monoxide as well as the reduction of nitrogen oxides to nitrogen.
- CARB California Air Resource Board
- ULEV ultra-low emission vehicle
- FTP U.S. Federal Test Procedure
- a typical motor vehicle catalyst is an underfloor TWC catalyst which catalyzes the oxidation by oxygen in the exhaust gas of the unburned hydrocarbons and carbon monoxide and the reduction ofnitrogen oxides to nitrogen.
- TWC catalysts which exhibit good activity and long life comprise one or more precious metal components, e.g., platinum group metal components such as platinum, palladium, rhodium, ruthenium and iridium located upon a high surface area, refractory oxide support, e.g., a high surface area alumina coating.
- the support is carried on a suitable carrier or substrate such as a monolithic carrier comprising a refractory ceramic or metal honeycomb structure, or refractory particles such as spheres or short, extruded segments of a suitable refractory material.
- U.S. Patent No. 4,134,860 relates to the manufacture of catalyst structures.
- the catalyst composition can contain platinum group metals, base metals, rare earth metals and refractory, such as alumina support.
- the composition can be deposited on a relatively inert carrier such as a honeycomb.
- the high surface area alumina support materials also referred to as "gamma alumina” or “activated alumina,” typically exhibit a BET surface area in excess of 60 square meters per gram ("m 2 /g"), often up to about 200 m 2 /g or more.
- Such activated alumina is usually a mixture of the gamma and delta phases of alumina, but may also contain substantial amounts of eta, kappa and theta alumina phases. It is disclosed to utilize refractory metal oxides otherthan activated alumina as a support for at least some of the catalytic components in a given catalyst. For example, bulk ceria, zirconia, alpha alumina and other materials are known for such use. Although many of these materials suffer from the disadvantage of having a considerably lower BET surface area than activated alumina, that disadvantage tends to be offset by a greater durability of the resulting catalyst.
- exhaust gas temperatures can reach 1000°C, and such elevated temperatures cause the activated alumina (or other) support material to undergo thermal degradation caused by a phase transition with accompanying volume shrinkage, especially in the presence of steam, whereby the catalytic metal becomes occluded in the shrunken support medium with a loss of exposed catalyst surface area and a corresponding decrease in catalytic activity.
- alumina supports against such thermal degradation by the use of materials such as zirconia, titania, alkaline earth metal oxides such as baria, calcia or strontia or rare earth metal oxides, such as ceria, lanthana and mixtures of two or more rare earth metal oxides.
- materials such as zirconia, titania, alkaline earth metal oxides such as baria, calcia or strontia or rare earth metal oxides, such as ceria, lanthana and mixtures of two or more rare earth metal oxides.
- ceria Bulk cerium oxide
- ceria is disclosed to provide an excellent refractory oxide support for platinum group metals other than rhodium, and enables the attainment of highly dispersed, small crystallites of platinum on the ceria particles, and that the bulk ceria may be stabilized by impregnation with a solution of an aluminum compound, followed by calcination.
- U.S. Patent 4,714,694 of C.Z. Wan et al. discloses aluminum-stabilized bulk ceria, optionally combined with an activated alumina, to serve as a refractory oxide support for platinum group metal components impregnated thereon.
- U.S. Patent No. 4,923,842 discloses a catalytic composition for treating exhaust gases comprising a first support having dispersed thereon at least one oxygen storage component and at least one noble metal component, and having dispersed immediately thereon an overlayer comprising lanthanum oxide and optionally a second support.
- the catalyst layer is separate from the lanthanum oxide.
- the noble metal can include platinum, palladium, rhodium, ruthenium and iridium.
- the oxygen storage component can include the oxide of a metal from the group consisting of iron, nickel, cobalt and the rare earths. Illustrative of these are cerium, lanthanum, neodymium, praseodymium, etc. Oxides of cerium and praseodymium are particularly useful as oxygen storage components.
- U.S. Patent No. 4,808,564 discloses a catalyst for the purification of exhaust gases having improved durability which comprises a support substrate, a catalyst carrier layer formed on the support substrate and catalyst ingredients carried on the catalyst carrier layer.
- the catalyst carrier layer comprises oxides of lanthanum and cerium in which the molar fraction of lanthanum atoms to total rare earth atoms is 0.05 to 0.20 and the ratio of the number of the total rare earth atoms to the number of aluminum atoms is 0.05 to 0.25.
- U.S. Patent No. 4,438,219 discloses an alumina-supported catalyst for use on a substrate.
- the catalyst is stable at high temperatures.
- the stabilizing material is disclosed to be one of several compounds including those derived from barium, silicon, rare earth metals, alkali and alkaline earth metals, boron, thorium, hafnium and zirconium.
- barium oxide, silicon dioxide and rare earth oxides which include lanthanum, cerium, praseodymium, neodymium, and others are indicated to be preferred. It is disclosed that contacting them with some calcined alumina film permits the calcined alumina film to retain a high surface area at higher temperatures.
- U. S. Patent Nos. 4,476,246 , 4,591,578 and 4,591,580 disclose three-way catalyst compositions comprising alumina, ceria, an alkali metal oxide promoter and noble metals.
- U.S. Patent No. 4,591,518 discloses a catalyst comprising an alumina support with components deposited thereon consisting essentially of a lanthana component, ceria, an alkali metal oxide and a platinum group metal.
- U.S. Patent No. 4,591,580 discloses an alumina-supported platinum group metal catalyst. The support is sequentially modified to include support stabilization by lanthana or lanthana rich rare earth oxides, double promotion by ceria and alkali metal oxides and optionally nickel oxide.
- Palladium-containing catalyst compositions see, e.g., U.S. PatentNo. 4,624,940 , have been found useful for high temperature applications.
- the combination of lanthanum and barium is found to provide a superior hydrothermal stabilization of alumina which supports the catalytic component, palladium.
- U.S. Patent No. 4,780,447 discloses a catalyst which is capable of controlling HC, CO and NO x as well as H 2 S in emissions from the tailpipe of catalytic converter-equipped automobiles.
- the use of the oxides of nickel and/or iron is disclosed as a hydrogen sulfide gettering-type of compound.
- U.S. Pat. No. 4,965,243 discloses a method to improve thermal stability of a TWC catalyst containing precious metals by incorporating a barium compound and a zirconium compound together with ceria and alumina. This is stated to form a catalytic moiety to enhance stability of the alumina washcoat upon exposure to high temperature.
- J01210032 discloses a catalytic composition comprising palladium, rhodium, active alumina, a cerium compound, a strontium compound and a zirconium compound. These patents suggest the utility of alkaline earth metals in combination with ceria, zirconias to form a thermally-stable alumina-supported pauadium-containing washcoat.
- U.S. Patents 4,624,940 and 5,057,483 refer to ceria-zirconia containing particles. It is found that ceria can be dispersed homogeneously throughout the zirconia matrix up to 30 weight percent of the total weight of the ceria-zirconia composite to form a solid solution. A co-formed (e.g., co-precipitated) ceria oxide-zircoma particulate composite can enhance the ceria utility in particles containing ceria-zirconia mixture.
- the ceria provides the zirconia stabilization and also acts as an oxygen storage component
- the '483 patent discloses that neodymium and/or yttrium can be added to the ceria-zirconia composite to modify the resultant oxide properties as desired.
- U.S. Patent 4,504,598 discloses a process for producing a high temperature resistant TWC catalyst.
- the process includes forming an aqueous slurry of particles of a gamma or activated alumina and impregnating the alumina with soluble salts of selected metals including cerium, zirconium, at least one of iron and nickel and at least one of platinum, palladium and rhodium and, optionally, at least one of neodymium, lanthanum, and praseodymium.
- the impregnated alumina is calcined at 600 °C and then dispersed in water to prepare a slurry which is coated on a honeycomb carrier and dried to obtain a finished catalyst.
- U.S. Patent No. 4,587,231 discloses a method of producing a monolithic three-way catalyst for the purification of exhaust gases.
- a mixed oxide coating is provided to a monolithic carrier by treating the carrier with a coating slip in which an active alumina powder containing cerium oxide is dispersed together with a ceria powder and then baking the treated carrier,
- platinum, rhodium and/or palladium are deposited on the oxide coating by thermal decomposition.
- a zirconia powder may be added to the coating slip.
- U.S. Patent No 5,075,296 discloses dispersing an alumina washcoat on a carrier and then dipping the carrier having the washcoat into an aqueous solution containing zirconium, cerium and rare earth (including samarium). Thereafter, the carrier is contained to form a cerium-zirconium-samarium composite on the surface of the carrier and the underlying alumina particles.
- the present invention relates to a catalyst composition containing a composite of cerium, zirconium and samarium components as well as the use of such catalyst composition for the treatment of a gas stream to reduce contaminants contained therein.
- the catalyst composition which may be utilized in a close-coupled and/or medium-coupled mode adjacent to or near the exhaust manifold of the engine, and/or in a catalytic converter located "under the floor" of the vehicle downstream of the exhaust manifold.
- the catalyst composition may be utilized in the form of a single or multiple bricks, a single or multiple canisters, etc.
- the particular mode i.e., placement in respect to the exhaust manifold of the engine
- usage of the catalyst composition in the form of single or multiple bricks or canisters will depend on various factors such as the level of pollutants in the exhaust gas stream at the outset, desired maximum level of pollutants at the cold start phase of engine operation, auxiliary mechanical emission control devices such as air pumps, engine/exhaust architecture, etc.
- the catalyst composition of the invention is designed to reduce pollutants in automotive engine exhaust gas streams at temperatures as low as 350 °C, preferably as low as 300°C and more preferably as low as 200°C.
- the catalyst composition of the present comprises components which catalyze low temperature reactions. This is indicated by the light-off temperature.
- the light-off temperature for a specific component is the temperature at which 50% of that component reacts. It has been found that the catalyst compositions of the present invention provide for significant improvements in nitrogen oxides conversion as well as lower light-off temperatures in comparison to prior art TWC catalyst compositions.
- the catalyst compositions of the invention are thermally stable upon exposure to temperatures up to 1100°C and higher during the operating life of the engine. At the same time, the catalyst composition of the invention provides a relatively high hydrocarbon conversion rate as well as a high rate of conversion of nitrogen oxides to nitrogen.
- the catalyst composition of the present invention is set out in claim 1. Preferred features are set out in claims 2 to 18. The method of the present invention is set out in claim 19. Preferred features are set out in claims 20 to 36.
- the composite comprises a cerium component, a zirconium component and a samarium component.
- the composite is in the form of a particulate oxide composite which comprises ceria, zirconia and samaria.
- the cerium component is present in the amount of 10 to 90 wt.%, preferably 15 to 70 wt.%
- the zirconium component is present in the amount of 10 to 90wt.%, preferably 15 to 70 wt%
- the samarium component is present in the amount of 1 to 40 wt.%, preferably 7 to 20 wt.%, based on the weight of the composite.
- the catalyst composition of the present invention comprises a mixture of (a) the foregoing composite, (b) a catalytically effective amount of at least one precious metal component and (c) a refractory metal oxide support.
- the catalyst composition is disposed on a carrier, typically a metal or honeycomb, in a desired amount.
- the catalyst composition plus the support may comprise about 2 to about 50 wt.%, preferably 5 to 20 wt%, based on the weight of the finished carrier, i. e., the weight of the catalyst composition plus the weight of the support plus the weight of the carrier.
- the composite will be present in the amount of 0.0006 to 0.18 g/cm 3 (0.01 to 3 g/in 3 ), preferably 0.006 to 0.06 g/cm 3 (0.1 to 1 g/in 3 ), of the carrier.
- the precious metal component is formed as a layer or coating upon the support and the resultant coated support is then mixed with the composite.
- the mixture of the precious metal-coated support and the composite is then deposited upon the carrier generally as a coated layer over most, if not all, of the surfaces of the carrier contacted.
- the combined structure i.e., the mixture of the precious metal-coated support and the composite plus carrier, is then dried at a temperature of about 110°C for 2 to 5 hours and calcined in air at a temperature of 400 to 600°C.
- any suitable carrier may be used for the catalyst composition such as a monolithic carrier having a honeycomb structure, i.e., a plurality of gas flow passages extending therethrough from an inlet or an outlet face of the carrier, so that the passages are open to fluid flow therethrough,
- the passages are defined by walls on which the catalytic material is coated as a "washcoat" so that the gases slowing through the passages will contact the catalytic material.
- the flow passages of the monolithic carrier are thin-walled channels which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc.
- Such structures may contain from about 9.3 (60) to about 108.5 (700) or more, usually about 31 to 62 (200 to 400), gas inlet openings ("cells") per cm 2 (square inch) of cross section.
- the amounts of the various components are presented based on grams per volume.
- the amounts of ingredients are conventionally expressed as grams per cubic metre (g/m 3 ) (grams per cubic foot (g/ft 3 )) of the carrier for the precious metal component(s) and grams per cubic centimeter (g/cm 3 ) (grams per cubic inch (g/in 3 )) of the carrier for the other ingredients (i.e., the composite and the support) as this measure accommodates different gas flow passage cell sizes in different monolithic carrier substrates.
- the carrier may comprise a refractory ceramic or metal having a honeycomb structure.
- Suitable refractory ceramic materials include alumina, silica, titania and zirconia compounds, e.g., cordierite (which is preferred), cordietite-alpha alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircon petalite, alpha alumina and aluminosilicates.
- a metallic honeycomb may be made of a refractory metal such as stainless steel or other suitable iron-based corrosion-resistant alloys.
- the refractory metal oxide support includes materials such as activated compounds selected from the group consisting of alumina (which is preferred), silica, titania, silica-alumina, alumina-silicates, alumina-zirconia, alumina-chromia, alumina-ceria and mixtures thereof.
- the refractory metal oxide support will be present in the amount of 0.006 to 0.24 g/cm 3 (0.1 to 4.0 g/in 3 ) of carrier and will be present in the form of finely divided, high surface area particles having a particle size above 10-15 micrometers.
- the activated alumina is thermally stabilized to retard undesirable alumina phase transformations from gamma to alpha at elevated temperatures by doping the activated alumina with a rare earth component such as lanthanum (preferred) or neodymium or mixtures thereof in an amount of about 0.0012 to about 0.0305 g/cm 3 (about 0.02 to about 0.5 g/in 3 ) of carrier.
- a rare earth component such as lanthanum (preferred) or neodymium or mixtures thereof in an amount of about 0.0012 to about 0.0305 g/cm 3 (about 0.02 to about 0.5 g/in 3 ) of carrier.
- the precious metal component of the catalyst composition comprises one or more metals selected from the group consisting of gold, silver and platinum group metals.
- Platinum group metals include platinum, palladium, rhodium, ruthenium and iridium components and mixtures thereof
- the precious metal component(s) are typically present in the amount of 3.53 to 8830 g/m 3 (0.1 to 250 g/ft 3 ), preferably 17.6 to 3530 g/m 3 (0.5 to 100 g/ft 3 ) of the carrier.
- the preferred precious metal components are platinum, rhodium or a mixture of platinum and rhodium metal components which are typically present in a platinum:rhodium ratio of 0.1:1 to 20:1, preferably 1:1 to 10:1.
- a process which can be used to prepare the composite of the present invention starts with the preparation of a zirconium hydroxide sol.
- This sol can be prepared by precipitating zirconium sulfate with sodium hydroxide at high temperatures reflux, typically from 90 to 100°C to make nanometer-size crystals (typically up to 100 nanozneters), Impurities, e.g., sodium, sulfur, etc. can be washed out with an aqueous liquid.
- An acid e.g., nitric acid, can be used to break up the aggregates to obtain the zirconium hydroxide sol and to reduce the pH of the liquid.
- the cerium and samarium components in the form of salts such as nitrates are added.
- the composite sol should be sufficiently acidic, e.g., a pH of 0.5 to 3, preferably, 0.5 to 2,0, at this point in order to keep the salts in solution.
- the pH can then be quickly increased, e.g., with ammonia, to precipitate the composite compounds.
- the formation of large aggregates is preferably avoided by controlling the pH.
- the precipitated composite can then be washed with an aqueous liquid such as deionized water and dried at suitable conditions in air in an oven at temperatures of up to 250°C, typically at 150°C, for as long as necessary, usually overnight.
- the precipitated composite can then be calcined in air at elevated temperatures to convert the composite to particulate oxide composite which comprises ceria, zirconia and samaria.
- the calcination process is typically carried out at a temperature of 450 to 750°C, preferably 550°C for 0.5 to 10 hours, preferably 2 hours.
- the resultant composite of ceria, zirconia and samaria may then be mixed with the precious metal component which has been preferably disposed, i,e., layered or coated, on the refractory metal oxide support.
- the catalyst composition may be prepared by mixing the composite prepared as set forth above with the precious metal component and the refractory metal oxide support in the form of an aqueous slurry, comminuting the slurry (i.e., by ball milling), mixing the comminuted slurry with the carrier followed by drying and calcination.
- the composite be mixed with the precious metal component which has been previously disposed on the refractory metal oxide support.
- the precious metal component(s) disposed on the refractory metal oxide support may be prepared in the following manner which involves the preparation of an aqueous slurry of the precious metal component(s) and the refractory metal oxide support.
- the method involves fixing the precious metal component(s) onto at least one support.
- the fixing step can be any of the suitable fixing steps known in the prior art such as chemical or thermal fixing.
- a preferred fixing step is to thermally fix the precious metal component(s) to the support. This is preferably conducted in air at a temperature of 50 to 500°C for about 0.5 to about 2 hours.
- the refractive metal oxide support e.g., activated alumina
- the refractive metal oxide support is impregnated with an aqueous solution or dispersion of the precious metal component present as a compound or complex.
- the selected precious metal compound or complex should be one which, upon calcination or use thereof, decomposes or otherwise converts to a catalytically active form, usually the metal or metal oxide.
- Water-soluble compounds or water-dispersible compounds or complexes of the metal component may be used as long as the liquid medium used to impregnate or deposit the metal component onto the refractory metal oxide support particles does not adversely react with the metal or its compound or its complex or other components which may be present in the catalyst composition and is capable ofbeing removed from the metal component by volatilization or decomposition upon heating and/or application of a vacuum. In some cases, the completion of removal of the liquid may not take place until the catalyst is placed into use and subj ected to the high temperatures encountered during operation. Generally, both from the point of view of economics and environmental aspects, aqueous solutions of soluble compounds or complexes of the platinum-group metals are preferred.
- suitable compounds are chloroplatinic acid, amine-solubilized platinum hydroxide, palladium nitrate or palladium chloride, rhodium chloride, rhodium nitrate, hexamine rhodium chloride, etc.
- platinum-group metal a compound thereof.
- a preferred method of preparing the catalyst composition of the invention is to prepare a mixture of a solution of at least one platinum-group metal, e.g., platinum amine complex and/or rhodium nitrate, and at least one finely divided, high surface area, refractory metal oxide support, e.g., activated alumina, which is sufficiently dry to absorb substantially all of the solution to form a slurry.
- the slurry is acidic, having a pH of about 2 to less than 7.
- the pH of the slurry may be lowered by the addition of a minor amount of an inorganic or organic acid such as acetic acid (preferred), hydrochloric acid or nitric acid, to the slurry.
- a refractory metal oxide support stabilizer e.g., lanthanum nitrate, and/or a binder, e.g., zirconia acetate, and/or an alkaline earth metal compound promoter, e.g., strontium nitrate, may be added to the slurry.
- a refractory metal oxide support stabilizer e.g., lanthanum nitrate
- a binder e.g., zirconia acetate
- an alkaline earth metal compound promoter e.g., strontium nitrate
- the slurry of the catalyst composition is thereafter comminuted.
- the comminution may be accomplished in a ball mill or other similar equipment for 4-8 hours with the result such that the final particle size will typically be that the final particle size will be 90% less than about 10 microns.
- This slurry can then be used to coat a macro size carrier preferably having a low surface area.
- a honeycomb carrier such as cordierite is immersed in the slurry and the coated honeycomb carrier is then placed in a drying oven and dried at about 110°C for about two to five hours. The dried honeycomb is then calcined in air at about 400-600°C for about one hour.
- MI-560 had a ceria content of 58.7 %, a zirconia content of 42.3% and trace amounts of Pr, La, Nd, Sm, Y Si, Na and S.
- This composite had a surface area of 138 m 2 /g and a surface area of 37 m 2 /g after being heated at 900°C for four hours.
- These ingredients were thoroughly mixed and 77.2g of an aqueous solution of a platinum amine solution were added dropwise into the mixture while stirring was maintained. Thereafter, 40 g of acetic acid were added to the mixture after the addition of the platinum solution was completed. Water was then added resulting in a solids concentration of 50% and a pH of 4-5.
- the resultant slurry was then placed in a 3.78 ⁇ 10 -3 m 2 (one-gallon) ball mill with 2000 g of ball media.
- the slurry was milled for about 6-8 hours and the final particle size of the comminuted slurry was 90% ⁇ 10 microns.
- the procedure was repeated for the rhodium slurry using 160 g of a mixture of equal amounts of high surface area (150 m 2 /g) and low surface area (90 m 2 /g) alumina, 160 g of a ceria-zirconia composite (20 Ce/80 Zr) prepared in accordance with U.S. Patent 5,898,014 , and 170 g of zirconium acetate solution (for use as a binder). A solution (29 g) of rhodium nitrate was used for this slurry.
- the Pt and Rh slurries were then mixed to form a final slurry having a solids content of 45-50%, a pH of 4-5 and a viscosity of 50-100 centipoise @ 20°C.
- a cordierite honeycomb having a diameter of 9.30 cm (3.66 inches), a length of 11.43 cm (4.5 inches), a cell density of 400 and a wall thickness of 0.16 mm (6.5 mil) was coated with this slurry by immersion and the channels were cleared of slurry residue by an air gun.
- the coated honeycomb was then placed in a drying oven and dried at 120°C for four to eight hours. Thereafter, the dried honeycomb was calcined in air at 500°C for 1 hour.
- honeycomb having a diameter of 3.81 cm (1.5 inches) and a length of 7.62 cm (3 inches) were used to prepare core samples.
- Catalyst bricks formed from reference catalyst A had a precious metal loading of 1413 g/m 3 (40 g/ft 3 ) and a PtRh ratio of 5:1.
- Example 1 was repeated using a cerium/zirconium/samarium composite obtained from W.R. Grace Co. with the product code designation of "MI-560-Sm".
- MI-560-Sm had a ceria content of 58.1%, a zirconia content of 42.3%, a samaria content of 9.2% and trace amounts of Pr, La, Nd, Sm, Y Si, Na and S.
- This composite had a surface area of 134 m 2 /g and a surface area of 38 m 2 /g after being heated at 900°C for four hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Claims (36)
- Katalysatorzusammensetzung abgeschieden auf einem Träger umfassend eine Mischung aus:(a) einem teilchenförmigen Oxidverbundstoff, welcher Cerdioxid, Zirkoniumdioxid und Samariumoxid (samaria) umfasst,(b) eine katalytisch wirksame Menge wenigstens eines Edelmetallbestandteiles und(c) ein teilchenförmigen feuerfesten Metalloxidträger,wobei der Verbundstoff in einer Menge von 0,0006 bis 0,18 g/cm3 (0,01 bis 3 g/in3) des Trägers vorhanden ist.
- Katalysatorzusammensetzung nach Anspruch 1, wobei das Cerdioxid in einer Menge von 10 bis 90 Gew.% vorhanden ist, das Zirkoniumdioxid in einer Menge von 10 bis 90 Gew.% vorhanden ist und das Samariumoxid in der Menge von ungefähr 1 bis ungefähr 40 Gew.% vorhanden ist, bezogen auf das Gewicht des Verbundstoffes.
- Katalysatorzusammensetzung nach Anspruch 2, wobei das Cerdioxid in der Menge von 15 bis 70 Gew.% vorhanden ist, das Zirkoniumdioxid in einer Menge von 15 bis 70 Gew.% vorhanden ist und das Samariumoxid in der Menge von 7 bis 20 Gew.% vorhanden ist, bezogen auf das Gewicht des Verbundstoffes.
- Katalytische Zusammensetzung nach Anspruch 1, wobei der Edelmetallbestandteil auf dem feuerfesten Metalloxidträger abgeschieden ist.
- Katalysatorzusammensetzung nach Anspruch 1, wobei der Verbundstoff in der Menge von 0,006 bis 0,06 g/cm3 (0,1 bis 1 g/in3) des Trägers vorhanden ist.
- Katalysatorzusammensetzung nach Anspruch 1, wobei der Edelmetallbestandteil ein Platinmetallbestandteil umfasst.
- Katalysatorzusammensetzung nach Anspruch 6, wobei der Platinmetallbestandteil gewählt ist aus der Gruppe bestehend aus Platin-, Palladium-, Rhodium-, Ruthenium-, Iridiumbestandteilen und deren Mischungen.
- Katalysatorzusammensetzung nach Anspruch 7, wobei der Platinmetallbestandteil Platinmetallbestandteile, Rhodiummetallbestandteile oder eine Mischung aus Platin- und Rhodiummetallbestandteilen umfasst.
- Katalysatorzusammensetzung nach Anspruch 8, wobei der Platinmetallbestandteil eine Mischung aus Platin- und Rhodiummetallbestandteilen umfasst und wobei das Verhältnis des Platinmetallbestandteils zu dem Rhodiummetallbestandteil in dem Bereich von 0.01:1 bis 20:1 liegt.
- Katalysatorzusammensetzung nach Anspruch 9, wobei das Verhältnis des Platinmetallbestandteils zu dem Rhodiummetallbestandteil in dem Bereich von 1:1 zu 10:1 liegt.
- Katalysatorzusammensetzung nach Anspruch 1, wobei der Edelmetallbestandteil in einer Menge von 3,53 bis 8830 g/m3 (0,1 bis 250 g/ft3) des Trägers vorhanden ist.
- Katalysatorzusammensetzung nach Anspruch 11, wobei der Edelmetallbestandteil in einer Menge von 17,6 bis 3530 g/m3 (0,5 bis 100 g/ft3) des Trägers vorhanden ist.
- Katalysatorzusammensetzung nach Anspruch 1, wobei der Träger ein monolithischer Träger ist, umfassend eine feuerfeste Keramik oder ein Metall mit einer Wabenstruktur.
- Katalysatorzusammensetzung nach Anspruch 13, wobei der Träger Cordierit umfasst.
- Katalysatorzusammensetzung nach Anspruch 1, wobei der Metalloxidträger gewählt ist aus der Gruppe bestehend aus Aluminiumoxid, Siliziumdioxid, Titandioxid und Zirkoniumdioxidverbindungen.
- Katalysatorzusammensetzung nach Anspruch 15, wobei der feuerfeste Metalloxidträger gewählt ist aus der Gruppe bestehend aus aktivierten Verbindungen, gewählt aus der Gruppe bestehend aus Aluminiumoxid, Siliziumdioxid, Titandioxid, Siliziumdioxid-Aluminiumoxid, Aluminiumoxid-Silikaten, Aluminiumoxid-Zirkoniumdioxid, Aluminiumoxid-Chromoxid, Aluminiumoxid-Cerdioxid und deren Mischungen.
- Katalysatorzusammensetzung nach Anspruch 16, wobei der feuerfeste Metalloxidträger aktiviertes Aluminiumoxid umfasst.
- Katalysatorzusammensetzung nach Anspruch 17, wobei das aktivierte Aluminiumoxid in einer Menge von 0,006 bis 0,24 g/cm3 (0,1 bis 4,0 g/in3) des Trägers vorhanden ist.
- Verfahren zur Behandlung eines Gasstromes umfassend Kohlenwasserstoffe, Kohlenstoffmonoxid und Stickstoffoxide, umfassend(a) Fließen des Gasstromes zu einem Katalysatorelement umfassend eine Katalysatorzusammensetzung umfassend eine Mischung aus:(i) einem teilchenförmigen Oxidverbundstoff, welcher Cerdioxid, Zirkoniumdioxid und Samariumoxid umfasst,(ii) eine katalytisch wirksame Menge eines Edelmetallbestandteils, und(iii) einen teilchenförmigen feuerfesten Metalloxidträger,wobei die Katalysatorzusammensetzung auf einem Träger abgeschieden ist und der Verbundstoff in einer Menge von 0,0006 bis 0,18 g/cm3 (0,1 bis 3 g/in3) des Trägers vorhanden ist; und(b) katalytisches Oxidieren der Kohlenwasserstoffe und des Kohlenstoffmonoxids und katalytisches Reduzieren der Stickstoffoxide in dem Gas in Anwesenheit des Katalysatorelementes.
- Verfahren nach Anspruch 19, wobei Cerdioxid in der Menge von 10 bis 90 Gew.% vorhanden ist, Zirkoniumdioxid in der Menge von 10 bis 90 Gew.% vorhanden ist, und das Samariumoxid in der Menge von 1 bis 40 Gew.% vorhanden ist, bezogen auf das Gewicht des Verbundstoffes.
- Verfahren nach Anspruch 20, wobei das Cerdioxid in der Menge von 15 bis 70 Gew.% vorhanden ist, das Zirkoniumdioxid in der Menge von 15 bis 70 Gew.% vorhanden ist, und das Samariumoxid in der Menge von 7 bis 20 Gew.% vorhanden ist, bezogen auf das Gewicht des Verbundstoffes.
- Verfahren nach Anspruch 19, wobei der Edelmetallbestandteil auf dem feuerfesten Metalloxidträger aufgebracht ist.
- Verfahren nach Anspruch 19, wobei der Verbund in der Menge von 0,006 bis 0,06 g/in3 (0,1 bis 1 g/in3) des Trägers vorhanden ist.
- Verfahren nach Anspruch 19, wobei der Edelmetallbestandteil ein Platinmetallbestandteil umfasst.
- Verfahren Anspruch 24, wobei der Platinmetallbestandteil gewählt ist aus der Gruppe bestehend aus Platin-, Palladium-, Rhodium-, Ruthenium- und Iridiumbestandteilen und deren Mischungen.
- Verfahren nach Anspruch 25, wobei der Platinmetallbestandteil Platinmetallbestandteile, Rhodiummetallbestandteile oder eine Mischung aus Platin- und Rhodiummetallbestandteilen umfasst.
- Verfahren nach Anspruch 26, wobei der Platinmetallbestandteil eine Mischung aus Platin- und Rhodiummetallbestandteilen umfasst und das Verhältnis des Platinmetallbestandteils zu dem Rhodiummetallbestandteil in dem Bereich von 0,01:1 zu 20:1 liegt.
- Verfahren nach Anspruch 27, wobei das Verhältnis des Platinmetallbestandteils zu dem Rhodiummetallbestandteil in dem Bereich von 1:1 zu 10:1 liegt.
- Verfahren nach Anspruch 26, wobei der Edelmetallbestandteil in einer Menge von 3,53 bis 8830 g/m3 (0,1 bis 250 g/ft3) des Trägers vorhanden ist.
- Verfahren nach Anspruch 29, wobei der Edelmetallbestandteil in einer Menge von 17 bis 3530 g/m3 (0,5 bis 100 g/ft3) des Trägers vorhanden ist.
- Verfahren nach Anspruch 19, wobei der Träger ein monolithischer Träger ist, umfassend eine feuerfeste Keramik oder Metall mit einer Wabenstruktur.
- Verfahren nach Anspruch 31, wobei der Träger Cordierit umfasst.
- Verfahren nach Anspruch 19, wobei der feuerfeste Metalloxidträger gewählt ist aus der Gruppe bestehend aus Aluminiumoxid-, Siliziumdioxid-, Titandioxid- und Zirkoniumdioxidverbindungen.
- Verfahren nach Anspruch 33, wobei der feuerfeste Metalloxidträger gewählt ist aus der Gruppe bestehend aus aktivierten Verbindungen, gewählt aus der Gruppe bestehend aus Aluminiumoxid, Siliziumdioxid, Titandioxid, Siliziumdioxid-Aluminiumoxid, Aluminiumoxid-Silikaten, Aluminiumoxid-Zirkoniumdioxid, Aluminiumoxid-Chromoxid, Aluminiumoxid-Cerdioxid und deren Mischungen.
- Verfahren nach Anspruch 34, wobei der feuerfeste Metalloxidträger aktiviertes Aluminiumoxid umfasst.
- Verfahren nach Anspruch 35, wobei das aktivierte Aluminiumoxid in einer Menge von 0,006 bis 0,24 g/in3 (0,1 bis 4,0 g/in3) des Trägers vorhanden ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US663312 | 2000-09-15 | ||
US09/663,312 US6492297B1 (en) | 2000-09-15 | 2000-09-15 | Catalyst composition for purifying exhaust gas |
PCT/US2001/028074 WO2002022242A1 (en) | 2000-09-15 | 2001-09-07 | Catalyst composition for purifying exhaust gas |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1333909A1 EP1333909A1 (de) | 2003-08-13 |
EP1333909B1 true EP1333909B1 (de) | 2008-04-23 |
Family
ID=24661276
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01970694A Expired - Lifetime EP1333909B1 (de) | 2000-09-15 | 2001-09-07 | Katalysatorzusammensetzung zur reinigung von abgasen |
Country Status (12)
Country | Link |
---|---|
US (2) | US6492297B1 (de) |
EP (1) | EP1333909B1 (de) |
JP (1) | JP4292005B2 (de) |
KR (1) | KR100795267B1 (de) |
AT (1) | ATE392944T1 (de) |
AU (1) | AU2001290673A1 (de) |
DE (1) | DE60133760T2 (de) |
DK (1) | DK1333909T3 (de) |
ES (1) | ES2305105T3 (de) |
PT (1) | PT1333909E (de) |
WO (1) | WO2002022242A1 (de) |
ZA (1) | ZA200302090B (de) |
Families Citing this family (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6864214B2 (en) * | 2000-09-26 | 2005-03-08 | Daihatsu Motor Co., Ltd. | Exhaust gas purifying catalyst |
EP1199096A1 (de) * | 2000-10-21 | 2002-04-24 | Degussa AG | Katalysator um Emission von organischen Verbindungen, Kohlenmonoxid und halogenierten organischen Verbindungen zu zersetzen |
JP2002177781A (ja) * | 2000-12-12 | 2002-06-25 | Ict:Kk | 排ガス浄化用触媒 |
JP4648567B2 (ja) * | 2001-05-11 | 2011-03-09 | Jx日鉱日石エネルギー株式会社 | オートサーマルリフォーミング触媒および燃料電池用燃料ガスの製造方法 |
JP4648566B2 (ja) * | 2001-05-11 | 2011-03-09 | Jx日鉱日石エネルギー株式会社 | オートサーマルリフォーミング触媒および燃料電池用燃料ガスの製造方法 |
JP3845274B2 (ja) * | 2001-06-26 | 2006-11-15 | ダイハツ工業株式会社 | 排ガス浄化用触媒 |
US7247597B2 (en) * | 2001-08-30 | 2007-07-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite oxide, process for producing the same, and exhaust gas reducing co-catalyst |
EP1287889B1 (de) * | 2001-09-03 | 2012-11-14 | Nissan Motor Co., Ltd. | Katalysator zur selektiven Oxidation von Kohlenmonoxid |
JP3758601B2 (ja) * | 2002-05-15 | 2006-03-22 | トヨタ自動車株式会社 | 吸蔵還元型NOx浄化用触媒 |
US7504355B2 (en) * | 2002-06-20 | 2009-03-17 | Princeton University | Supported metal catalyst with improved thermal stability |
JP4584555B2 (ja) * | 2002-10-17 | 2010-11-24 | 株式会社デンソー | セラミック触媒体 |
US6660683B1 (en) * | 2002-10-21 | 2003-12-09 | W.R. Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
JP3797313B2 (ja) | 2002-10-28 | 2006-07-19 | トヨタ自動車株式会社 | 金属酸化物粒子の製造法及び排ガス浄化用触媒 |
US20040180782A1 (en) * | 2003-03-10 | 2004-09-16 | Cataler Corporation | Exhaust-gas purifying catalyst |
US7030055B2 (en) * | 2003-08-18 | 2006-04-18 | W.R. Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
US20050100494A1 (en) | 2003-11-06 | 2005-05-12 | George Yaluris | Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking |
DE102004024026A1 (de) * | 2004-03-11 | 2005-09-29 | W.C. Heraeus Gmbh | Katalysator zur N2O-Zersetzung beim Ostwaldprozess |
JP3795895B2 (ja) * | 2004-03-25 | 2006-07-12 | 田中貴金属工業株式会社 | 触媒の製造方法 |
US7811961B2 (en) * | 2004-08-12 | 2010-10-12 | Ford Global Technologies, Llc | Methods and formulations for enhancing NH3 adsorption capacity of selective catalytic reduction catalysts |
EP1786560A4 (de) * | 2004-09-01 | 2010-09-29 | Emisense Technologies Llc | Keramikkatalysator für nox-oxidation und nox-umwandlung in emissionskontrollsystemen |
EP1632288B1 (de) * | 2004-09-03 | 2012-06-20 | Mazda Motor Corporation | Abgasreinigungskatalysator und Sauerstoffspeicherkomponente dafür |
DE102004043421A1 (de) * | 2004-09-06 | 2006-03-23 | W.C. Heraeus Gmbh | Katalysator für 2-Takt-Motoren oder Kleinmotoren |
CN1917957B (zh) | 2004-12-20 | 2014-07-30 | 田中贵金属工业株式会社 | 柴油机排气处理用的燃烧催化剂以及柴油机排气的处理方法 |
KR100665606B1 (ko) * | 2005-04-14 | 2007-01-09 | 희성엥겔하드주식회사 | 내연기관 배기가스 정화용 촉매조성물 제조용 400ppm 이상 이리듐 성분이 불순물로 포함된 로듐용액 |
JP5021188B2 (ja) * | 2005-08-01 | 2012-09-05 | 株式会社キャタラー | 排ガス浄化用触媒 |
JP4686316B2 (ja) * | 2005-09-27 | 2011-05-25 | 田中貴金属工業株式会社 | 触媒の製造方法 |
JP4835193B2 (ja) | 2006-02-20 | 2011-12-14 | マツダ株式会社 | ディーゼルパティキュレートフィルタ |
US7749472B2 (en) * | 2006-08-14 | 2010-07-06 | Basf Corporation | Phosgard, a new way to improve poison resistance in three-way catalyst applications |
US7550124B2 (en) * | 2006-08-21 | 2009-06-23 | Basf Catalysts Llc | Layered catalyst composite |
US7758834B2 (en) * | 2006-08-21 | 2010-07-20 | Basf Corporation | Layered catalyst composite |
US7820583B2 (en) * | 2006-08-24 | 2010-10-26 | Millennium Inorganic Chemicals, Inc. | Nanocomposite particle and process of preparing the same |
TWI449572B (zh) * | 2006-11-29 | 2014-08-21 | Umicore Shokubai Japan Co Ltd | Oxidation catalyst and the oxidation catalyst using an exhaust gas purification system |
EP2055367A3 (de) * | 2007-01-25 | 2009-05-27 | Nissan Motor Co., Ltd. | Abgasreinigungskatalysator und zugehöriges Herstellungsverfahren |
US8007750B2 (en) | 2007-07-19 | 2011-08-30 | Basf Corporation | Multilayered catalyst compositions |
US8038951B2 (en) | 2007-08-09 | 2011-10-18 | Basf Corporation | Catalyst compositions |
US7922988B2 (en) * | 2007-08-09 | 2011-04-12 | Michel Deeba | Multilayered catalyst compositions |
US7622096B2 (en) * | 2007-08-09 | 2009-11-24 | Basf Catalysts Llc | Multilayered catalyst compositions |
US7879755B2 (en) * | 2007-08-09 | 2011-02-01 | Basf Corporation | Catalyst compositions |
US20090175773A1 (en) * | 2008-01-08 | 2009-07-09 | Chen Shau-Lin F | Multilayered Catalyst Compositions |
US8038954B2 (en) * | 2008-02-14 | 2011-10-18 | Basf Corporation | CSF with low platinum/palladium ratios |
US8568675B2 (en) * | 2009-02-20 | 2013-10-29 | Basf Corporation | Palladium-supported catalyst composites |
US8940242B2 (en) * | 2009-04-17 | 2015-01-27 | Basf Corporation | Multi-zoned catalyst compositions |
US8530372B2 (en) * | 2009-07-22 | 2013-09-10 | Basf Corporation | Oxygen storage catalyst with decreased ceria reduction temperature |
US8758695B2 (en) * | 2009-08-05 | 2014-06-24 | Basf Se | Treatment system for gasoline engine exhaust gas |
US20110209466A1 (en) * | 2010-02-26 | 2011-09-01 | General Electric Company | Catalyst composition and catalytic reduction system comprising yttrium |
JP5567923B2 (ja) * | 2010-07-23 | 2014-08-06 | トヨタ自動車株式会社 | 排ガス浄化用触媒 |
KR101106973B1 (ko) * | 2011-07-05 | 2012-01-19 | 에프피지코리아(주) | 가압식 소화기 |
JP2015047517A (ja) | 2013-08-29 | 2015-03-16 | マツダ株式会社 | 排気ガス浄化用触媒及びその製造方法 |
EP3277410A4 (de) * | 2015-03-24 | 2019-02-20 | Tecogen, Inc. | Giftresistenter katalysator und systeme damit |
JP6698602B2 (ja) | 2017-09-27 | 2020-05-27 | イビデン株式会社 | 排ガス浄化用ハニカム触媒 |
JP6684257B2 (ja) | 2017-09-27 | 2020-04-22 | イビデン株式会社 | 排ガス浄化用ハニカム触媒 |
JP2019058875A (ja) | 2017-09-27 | 2019-04-18 | イビデン株式会社 | ハニカム触媒 |
JP2019058876A (ja) * | 2017-09-27 | 2019-04-18 | イビデン株式会社 | ハニカム触媒 |
WO2020041289A1 (en) | 2018-08-20 | 2020-02-27 | University Of Florida Research Foundation | Single-atom-based catalyst systems |
GB201901560D0 (en) * | 2019-02-05 | 2019-03-27 | Magnesium Elektron Ltd | Zirconium based dispersion for use in coating filters |
US11772078B2 (en) * | 2022-01-21 | 2023-10-03 | GM Global Technology Operations LLC | Layered catalyst structures and methods of making the same |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049583A (en) * | 1974-04-25 | 1977-09-20 | E. I. Du Pont De Nemours And Company | Metal oxide catalytic compositions having perovskite crystal structures and containing metals of the platinum group |
JPH0675676B2 (ja) | 1986-12-24 | 1994-09-28 | トヨタ自動車株式会社 | 排気ガス浄化用触媒 |
DE3853258T2 (de) | 1987-11-07 | 1995-08-24 | Nippon Catalytic Chem Ind | Katalysator zur Abgasreinigung von Dieselmotoren. |
CA1334962C (en) | 1988-04-14 | 1995-03-28 | Tomohisa Ohata | Catalyst for purifying exhaust gas and method for production thereof |
JPH0644999B2 (ja) * | 1988-04-30 | 1994-06-15 | 株式会社豊田中央研究所 | 排気ガス浄化用触媒 |
US5286699A (en) | 1988-12-09 | 1994-02-15 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Exhaust gas purifying catalyst suppressing the generation of hydrogen sulfide and method of making the catalyst |
JP2773193B2 (ja) * | 1989-03-03 | 1998-07-09 | 住友電気工業株式会社 | 透光性イツトリア焼結体の製造方法 |
US5232890A (en) | 1990-01-02 | 1993-08-03 | Ganguli Partha S | Precious metal catalysts with oxygen-ion conducting support |
ZA909211B (en) | 1990-02-23 | 1991-09-25 | Grace W R & Co | High surface area ceria |
DE69226581T2 (de) * | 1991-09-12 | 1999-02-04 | Cosmo Oil Co. Ltd., Tokio/Tokyo | Katalysator zur Reduktion von Stickoxiden |
FI90501C (fi) | 1992-02-13 | 1994-02-25 | Kemira Oy | Menetelmä tehostaa kolmitoimikatalysaattorin toimintaa |
DE69412780T2 (de) | 1994-01-28 | 1999-05-12 | Evangelos G. Patras Papadakis | Dreiwegkatalysator mit Pt, Rh und Pd, alle mit separatem Träger |
FR2730175B1 (fr) * | 1995-02-03 | 1997-04-04 | Inst Francais Du Petrole | Catalyseurs de reduction des oxydes d'azote en azote moleculaire dans un milieu surstoechiometrique en composes oxydants, procede de preparation et utilisations |
JP3386621B2 (ja) | 1995-03-30 | 2003-03-17 | トヨタ自動車株式会社 | ディーゼルエンジン用排ガス浄化触媒 |
US5837642A (en) | 1995-12-26 | 1998-11-17 | Daihatsu Motor Co., Ltd. | Heat-resistant oxide |
JPH09276703A (ja) | 1996-04-19 | 1997-10-28 | Honda Motor Co Ltd | 排気ガス浄化用触媒 |
US5898014A (en) | 1996-09-27 | 1999-04-27 | Engelhard Corporation | Catalyst composition containing oxygen storage components |
JP4053623B2 (ja) | 1996-12-27 | 2008-02-27 | 阿南化成株式会社 | ジルコニウム−セリウム系複合酸化物及びその製造方法 |
US6072074A (en) | 1998-05-08 | 2000-06-06 | Sumitomo Chemical Company Limited | Process for producing 3-propynyl-2-2-dimethylcycloprophane-carboxylic acid and its lower akyl esters |
-
2000
- 2000-09-15 US US09/663,312 patent/US6492297B1/en not_active Expired - Fee Related
-
2001
- 2001-09-07 KR KR1020037003822A patent/KR100795267B1/ko not_active IP Right Cessation
- 2001-09-07 ES ES01970694T patent/ES2305105T3/es not_active Expired - Lifetime
- 2001-09-07 JP JP2002526486A patent/JP4292005B2/ja not_active Expired - Fee Related
- 2001-09-07 EP EP01970694A patent/EP1333909B1/de not_active Expired - Lifetime
- 2001-09-07 AU AU2001290673A patent/AU2001290673A1/en not_active Abandoned
- 2001-09-07 PT PT01970694T patent/PT1333909E/pt unknown
- 2001-09-07 DE DE60133760T patent/DE60133760T2/de not_active Expired - Lifetime
- 2001-09-07 AT AT01970694T patent/ATE392944T1/de not_active IP Right Cessation
- 2001-09-07 WO PCT/US2001/028074 patent/WO2002022242A1/en active Application Filing
- 2001-09-07 DK DK01970694T patent/DK1333909T3/da active
-
2002
- 2002-11-15 US US10/295,307 patent/US7041263B2/en not_active Expired - Fee Related
-
2003
- 2003-03-14 ZA ZA200302090A patent/ZA200302090B/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE60133760T2 (de) | 2009-07-02 |
PT1333909E (pt) | 2008-06-16 |
ES2305105T3 (es) | 2008-11-01 |
US20030083194A1 (en) | 2003-05-01 |
EP1333909A1 (de) | 2003-08-13 |
DE60133760D1 (de) | 2008-06-05 |
DK1333909T3 (da) | 2008-07-14 |
JP2004508186A (ja) | 2004-03-18 |
KR20030034185A (ko) | 2003-05-01 |
KR100795267B1 (ko) | 2008-01-15 |
JP4292005B2 (ja) | 2009-07-08 |
ZA200302090B (en) | 2004-02-16 |
US6492297B1 (en) | 2002-12-10 |
WO2002022242A1 (en) | 2002-03-21 |
US7041263B2 (en) | 2006-05-09 |
ATE392944T1 (de) | 2008-05-15 |
AU2001290673A1 (en) | 2002-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1333909B1 (de) | Katalysatorzusammensetzung zur reinigung von abgasen | |
US6044644A (en) | Close coupled catalyst | |
EP0765189B1 (de) | Zusammengesetzter katalysator mit schichtstruktur | |
US5948377A (en) | Catalyst composition | |
EP0393612B1 (de) | Rhodium freier, Palladium und Platin enthaltender Katalysator auf mit Zirconiumoxid und/oder Lanthanoxid stabilisiertem Ceroxid | |
US5948723A (en) | Layered catalyst composite | |
US6248688B1 (en) | Catalyst composition containing oxygen storage components | |
US5898014A (en) | Catalyst composition containing oxygen storage components | |
US5981427A (en) | Catalyst composition | |
US6764665B2 (en) | Layered catalyst composite | |
US20020131914A1 (en) | Catalyst composition | |
JP3274688B2 (ja) | 分離した白金及びロジウム成分を含有する触媒組成物 | |
WO1993009146A2 (en) | High performance thermally stable catalyst | |
WO1992005861A1 (en) | Catalyst composition containing base metal oxide-promoted rhodium | |
EP0303495B1 (de) | Thermisch stabilisierte, Aluminiumoxid enthaltende Katalysatoren und Verfahren zur Herstellung derselben | |
MXPA97004170A (es) | Catalizador compacto |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20030408 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
17Q | First examination report despatched |
Effective date: 20060123 |
|
17Q | First examination report despatched |
Effective date: 20060123 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: BASF CATALYSTS LLC |
|
REF | Corresponds to: |
Ref document number: 60133760 Country of ref document: DE Date of ref document: 20080605 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20080530 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20080401640 Country of ref document: GR |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: HEPP WENGER RYFFEL AG |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: BASF CATALYSTS LLC Effective date: 20080521 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2305105 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD Ref country code: FR Ref legal event code: CA |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20081230 Year of fee payment: 8 Ref country code: IE Payment date: 20081224 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20081230 Year of fee payment: 8 Ref country code: PT Payment date: 20081219 Year of fee payment: 8 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20090126 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20090106 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 20081231 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CY Payment date: 20081231 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: MC Payment date: 20090108 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20090911 Year of fee payment: 9 Ref country code: GB Payment date: 20090902 Year of fee payment: 9 Ref country code: NL Payment date: 20090903 Year of fee payment: 9 Ref country code: SE Payment date: 20090910 Year of fee payment: 9 Ref country code: TR Payment date: 20090813 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20091006 Year of fee payment: 9 Ref country code: DE Payment date: 20090903 Year of fee payment: 9 Ref country code: ES Payment date: 20091006 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20090917 Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20100308 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100308 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090907 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20091012 Year of fee payment: 9 Ref country code: IT Payment date: 20090916 Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090907 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090907 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100406 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 |
|
BERE | Be: lapsed |
Owner name: BASF CATALYSTS LLC Effective date: 20100930 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20110401 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090907 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100907 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100907 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110531 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60133760 Country of ref document: DE Effective date: 20110401 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110401 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100907 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100907 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110401 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20111019 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100907 |